KR20180102132A - Liquid (meth) acrylic compositions comprising a multistage polymer and (meth) acrylic monomers, processes for their preparation, and uses thereof - Google Patents

Abstract

The present invention relates to liquid (meth) acrylic compositions comprising (meth) acrylic monomers, (meth) acrylic polymers and multistage polymers. In particular, the invention relates to liquid compositions comprising (meth) acrylic monomers, (meth) acrylic polymers and multistage polymers which can be used as syrups and in particular as syrups for impregnation. More particularly, the present invention is also directed to a process for preparing a liquid composition comprising a (meth) acrylic monomer, a (meth) acrylic polymer and a multistage polymer.

Description

Liquid (meth) acrylic compositions comprising a multistage polymer and (meth) acrylic monomers, processes for their preparation, and uses thereof

The present invention relates to liquid (meth) acrylic compositions comprising (meth) acrylic monomers, (meth) acrylic polymers and multistage polymers.

In particular, the invention relates to liquid compositions comprising (meth) acrylic monomers, (meth) acrylic polymers and multistage polymers which can be used as syrups and in particular as impregnating syrups.

More particularly, the present invention is also directed to a process for preparing a liquid composition comprising a (meth) acrylic monomer, a (meth) acrylic polymer and a multistage polymer.

[Technical Problem]

Impact modifiers are widely used to improve the impact strength on polymeric compositions for the purpose of compensating for their inherent brittleness or embrittlement, notch sensitivity and crack propagation, which occur at ambient temperatures, especially at sub-zero temperatures . Thus, the impact modified polymer is a polymeric material in which impact resistance and toughness are increased by incorporation of a top microdomain of a rubbery material.

This is typically due to the introduction of fine rubber particles into the polymer matrix which can absorb the energy of the impact and dissipate it. One possibility is to introduce rubber particles in the form of core-shell particles. These core-shell particles, which generally have a rubber core and a polymeric shell, are suitable for use with a rubber core for effective toughening and a suitable grafted shell grafted shell for compatibility and adhesion with the thermoplastic matrix Size.

The performance of impact modification is a function of particle size (especially of the rubber portion of the particles) and its amount. There is an optimum average particle size to have the highest impact strength with respect to the given amount of added impact modifier particles.

These primary impact modifier particles are generally added to the polymeric material in the form of powder particles. These powder particles are agglomerated primary impact modifier particles. During blending of the powder particles and the thermoplastic, the primary impact modifier particles are recovered and dispersed to a certain degree homogeneously in the thermoplastic material.

The particle size of the impact modifier particles is in the nanometer range, while the range of agglomerated powder particles is in the micrometer range. The latter is much easier to handle.

For many polymers, thermoplastic or thermoset polymers, it is very difficult or nearly impossible to accurately disperse such a multi-stage polymer in the form of core shell particles as agglomerated dry powder. The ideal homogeneous dispersion of the core-shell particles does not have aggregates after dispersion in the thermoplastic material (also the so-called matrix).

This is even more difficult when the multistage polymer is to be homogeneously distributed, for example, in a polymeric matrix comprising a fibrous substrate as the fiber reinforced polymeric composite.

The fibrous substrate is impregnated with a liquid composition, generally a liquid composition comprising monomers, oligomers and / or polymers or a molten polymer.

It is an object of the present invention to obtain a liquid composition comprising a (meth) acrylic monomer, a (meth) acrylic polymer and a multistage polymer, with a homogeneous dispersion of the multistage polymer.

It is also an object of the present invention to have a liquid composition comprising a (meth) acrylic monomer, a (meth) acrylic polymer and a multistage polymer, with a homogeneous dispersion of the multistage polymer, which can be used in the polymerization process.

It is a further object of the present invention to avoid or significantly reduce aggregation of the multistage polymer.

A further object is to have a process for the preparation of a liquid composition comprising a (meth) acrylic monomer, a (meth) acrylic polymer and a multistage polymer, with a homogeneous dispersion of the multistage polymer.

A still further object is the use of a composition comprising a monomer, (meth) acrylic polymer, for impact modification of the polymer.

A further object is to obtain a liquid composition comprising a (meth) acrylic monomer, a (meth) acrylic polymer and a multistage polymer, with a homogeneous dispersion of the multistage polymer, as the impregnating liquid for the fibrous substrate, The use of the liquid composition in an impregnation method for impregnation of a substrate.

It is yet another object of the present invention to wet the fibrous substrate in a fully, precisely, and homogeneous manner during impregnation with a liquid composition comprising a multistage polymer.

BACKGROUND OF THE INVENTION [

Document WO2014 / 013028 discloses impregnation methods for fibrous substrates, liquid (meth) acrylic syrups for impregnation methods, polymerization methods thereof and structured articles obtained therefrom. Syrups include (meth) acrylic monomers, (meth) acrylic polymers and optionally impact modifiers in the form of particulates.

Document WO2014 / 135815 discloses a viscous liquid (meth) acrylic syrup containing impact-reforming additives for enhancing the impact strength of thermoplastic materials obtained mainly from the polymerization of methacrylic or acrylic components and syrup. The impact-reforming additive is based on an elastomeric domain consisting of macromolecular blocks of flexible nature. In particular, multistage polymers in the form of core / shell particles are not disclosed.

Document WO2014 / 135816 discloses a viscous liquid (meth) acrylate syrup containing mainly an organic or mineral filler intended to reduce the proportion of methacrylic or acrylic components and residual monomer after polymerization of (meth) acrylic syrup. The organic filler is selected from crosslinked PMMA beads. In particular, multistage polymers in the form of core / shell particles are not disclosed.

None of the prior art documents discloses a composition as claimed, or a method of obtaining the same or its use.

Surprisingly, it has been found that a liquid composition comprising (i) is less viscous than a composition that does not comprise (meth) acrylic polymer (P1)

a) a (meth) acrylic polymer (P1),

b) a multistage polymer, and

c) (meth) acrylic monomer (M1),

Here, the weight ratio of the multistage polymer to the monomer (M1) in the liquid composition is 1/99 to 25/75.

Surprisingly, it has also been found that the liquid composition comprising (i) has a better dispersion of the multistage polymer than the composition which does not comprise the (meth) acrylic polymer (P1)

a) a (meth) acrylic polymer (P1),

b) a multistage polymer, and

c) (meth) acrylic monomer (M1),

Wherein the weight ratio of the multistage polymer to the monomer (M1) in the liquid composition is from 1/99 to 25/75.

Surprisingly, it has also been found that liquid compositions comprising (a) can be used to prepare dispersions of multistage polymers in monomers (M1) which are better than compositions that do not contain (meth) acrylic polymer (P1)

a) a (meth) acrylic polymer (P1),

b) a multistage polymer, and

c) (meth) acrylic monomer (M1),

Here, the weight ratio of the multistage polymer to the monomer (M1) in the liquid composition is 1/99 to 25/75.

Surprisingly, it has furthermore been found that the process for the preparation of a liquid composition comprising the steps of obtaining a liquid composition less viscous than a composition which does not comprise (meth) acrylic polymer (P1)

a) preparing a composition comprising a (meth) acrylic polymer (P1) and a multistage polymer,

b) mixing the composition of the previous step and (meth) acrylic monomer (M1)

Here, the weight ratio of the multistage polymer to the monomer (M1) in the liquid composition is 1/99 to 25/75.

Surprisingly, it has furthermore been found that the process for the preparation of a liquid composition, comprising the following steps, obtains an impregnating liquid in the form of a (meth) acrylic syrup:

a) preparing a composition comprising a (meth) acrylic polymer (P1) and a multistage polymer,

b) mixing the composition of the previous step and (meth) acrylic monomer (M1)

Here, the weight ratio of the multistage polymer to the monomer (M1) in the liquid composition is 1/99 to 25/75.

Surprisingly, it has also been found that liquid compositions comprising the following can be used for impregnation of fibrous substrates:

a) a (meth) acrylic polymer (P1),

b) a multistage polymer, and

c) (Meth) acrylic monomer (M1)

Wherein the multistage polymer to monomer weight ratio in the liquid composition is from 1/99 to 25/75.

Surprisingly, it has also been found that liquid compositions comprising the following can be used in the impregnation process for impregnation of fibrous substrates:

a) a (meth) acrylic polymer (P1),

b) a multistage polymer, and

c) (meth) acrylic monomer (M1),

Wherein the multistage polymer to monomer weight ratio in the liquid composition is 1/99 to 25/75 and the fibrous substrate is made of long fibers.

According to a first aspect, the present invention relates to a liquid composition comprising:

a) a (meth) acrylic polymer (P1),

b) a multistage polymer, and

c) (Meth) acrylic monomer (M1)

Wherein the multistage polymer to monomer weight ratio in the liquid composition is from 1/99 to 25/75.

According to a second aspect, the present invention relates to a process for preparing a liquid composition comprising the steps of:

a) preparing a composition comprising a (meth) acrylic polymer (P1) and a multistage polymer,

b) mixing the composition of the previous step and the (meth) acrylic monomer (M1)

Wherein the multistage polymer to monomer weight ratio in the liquid composition is from 1/99 to 25/75.

In a third aspect, the invention relates to the use of a liquid composition for impregnation of a fibrous substrate, comprising:

a) a (meth) acrylic polymer (P1),

b) a multistage polymer, and

c) (meth) acrylic monomer (M1),

Wherein the multistage polymer to monomer weight ratio in the liquid composition is from 1/99 to 25/75.

In a fourth aspect, the invention relates to the use of a liquid composition in an impregnation method for impregnation of a fibrous substrate, comprising:

a) a (meth) acrylic polymer (P1),

b) a multistage polymer, and

c) (meth) acrylic monomer (M1),

Wherein the multistage polymer to monomer weight ratio in the liquid composition is 1/99 to 25/75 and the fibrous substrate is made of long fibers.

The term "polymer powder" used herein refers to a polymer comprising powder grains in the range of at least 1 micrometer (占 퐉) obtained by agglomeration of a primary polymer comprising particles in the nanometer range.

The term "primary particle" used refers to a spherical polymer comprising particles in the nanometer range. Preferably, the weight average particle size of the primary particles is from 20 nm to 800 nm.

The term "particle size" used refers to the volume average diameter of the particles considered spherical.

The term "copolymer" used herein indicates that the polymer is composed of at least two different monomers.

The term "multistage polymer" used refers to a polymer formed in a sequential manner by a multistage polymerization process. One preferred method is a multi-stage emulsion polymerization wherein the first polymer is a first stage polymer and the second polymer is a second stage polymer, that is, the second polymer is prepared by emulsion polymerization in the presence of a first emulsion polymer .

The term "(meth) acrylic" used refers to all types of acrylic and methacrylic monomers.

The term "(meth) acrylic polymer" as used herein indicates that the (meth) acrylic polymer essentially comprises a polymer comprising (meth) acrylic monomers that make up more than 50 wt% of the (meth) acrylic polymer.

The term "epoxy resin" used is understood to be any organic compound having at least two functional groups of oxirane type that can be polymerized by ring opening.

The term "(meth) acrylic resin" used is understood as an adhesive based on acrylic and methacrylic monomers.

The term "masterbatch" used is understood to be a composition comprising the carrier material in a high concentration of the additive. The additive is dispersed in the carrier material.

The term "impact modifier " as used herein is understood as a material that, when incorporated into a polymeric material, increases the impact resistance and toughness of the polymeric material by means of a rubbery polymer or a top microdomain of the rubbery polymer.

The term "rubber" used refers to the thermodynamic state of the polymer in excess of its glass transition.

The term "rubber polymer" used refers to a polymer having a glass transition temperature (Tg) of less than 0 ° C.

The liquid composition of the present invention comprises at least three components a) (meth) acrylic polymer (P1), b) a multistage polymer, c) a (meth) acrylic monomer (M1) The multistage polymer to monomer weight ratio in the liquid composition in the composition is from 1/99 to 25/75.

Preferably, the weight ratio of the multistage polymer to the monomer (M1) in the liquid composition is from 2/98 to 24/76, more preferably from 3/97 to 23/77, even more preferably from 4/96 to 22/78, Lt; / RTI > to 20/80.

The dynamic viscosity of the liquid composition according to the invention is in the range of 10 mPa * s to 1 000 000 mPa * s, preferably 10 mPa * s to 500 000 mPa * s and advantageously 50 mPa * s to 300 000 mPa * s. The viscosity of a liquid composition (sometimes also referred to as syrup) can be easily measured by a flow meter with a shear rate of 0.1 s ^-1 to 100 s ^-1 . The dynamic viscosity is measured at 25 占 폚. In the case of shear thinning, the viscosity is measured at a shear rate of 1 s ^-1 .

With respect to the (meth) acrylic polymer (P1), its mass average molecular weight Mw is less than 100 000 g / mol, preferably less than 90 000 g / mol, more preferably less than 80 000 g / mol, / mol, advantageously less than 60 000 g / mol, more advantageously less than 50 000 g / mol, more advantageously less than 40 000 g / mol.

(Meth) acrylic polymer (P1), whose mass average molecular weight Mw is greater than 2 000 g / mol, preferably greater than 3000 g / mol, more preferably greater than 4000 g / mol, even more preferably greater than 5 000 g / mol, More advantageously greater than 6 000 g / mol, more advantageously greater than 6 500 g / mol, and even more advantageously greater than 7 000 g / mol and most advantageously greater than 10 000 g / mol.

The mass average molecular weight Mw of the (meth) acrylic polymer (P1) is from 2,000 g / mol to 100,000 g / mol, preferably from 3,000 g / mol to 90,000 g / mol, and more preferably from 4,000 g / mol to 80,000 g / / mol, advantageously from 5000 g / mol to 70 000 g / mol, more advantageously from 6 000 g / mol to 50 000 g / mol and most advantageously from 10 000 g / mol to 40 000 g / mol.

Preferably, the (meth) acrylic polymer (P1) is a copolymer comprising a (meth) acrylic monomer. More preferably, the (meth) acrylic polymer (P1) is a (meth) acrylic polymer. Even more preferably, the (meth) acrylic polymer (P1) comprises at least 50 wt% of a monomer selected from C1 to C12 alkyl (meth) acrylates. Advantageously, preferably the (meth) acrylic polymer (P1) comprises at least 50 wt% of a monomer selected from C1 to C4 alkyl methacrylates and C1 to C8 alkyl acrylate monomers and mixtures thereof.

Preferably, the (Tg) glass transition temperature of the (meth) acrylic polymer (P1) is from 30 캜 to 150 캜. The glass transition temperature of the (meth) acrylic polymer (P1) is more preferably 40 ° C to 150 ° C, advantageously 45 ° C to 150 ° C and more advantageously 50 ° C to 150 ° C.

Preferably, the polymer (meth) acrylic polymer (P1) is not crosslinked.

Preferably, the polymer (meth) acrylic polymer (P1) is not grafted onto any other polymer (s).

In a first preferred embodiment, the (meth) acrylic polymer P1 comprises from 50 wt% to 100 wt% methyl methacrylate, preferably from 80 wt% to 100 wt% methyl methacrylate, even more preferably from 80 wt% to 99.8 wt% Methyl methacrylate and 0.2 wt% to 20 wt% C1 to C8 alkyl acrylate monomers. Advantageously, the C1 to C8 alkyl acrylate monomers are selected from methyl acrylate, ethyl acrylate or butyl acrylate.

In a second preferred embodiment, the (meth) acrylic polymer (P1) comprises from 0 wt% to 50 wt% of a functional monomer. Preferably, the (meth) acrylic polymer (P1) comprises from 0 wt% to 30 wt% functional monomer, more preferably from 1 wt% to 30 wt%, even more preferably from 2 wt% to 30 wt%, advantageously from 3 wt% 30 wt.%, More advantageously from 5 wt.% To 30 wt.% And most advantageously from 5 wt.% To 30 wt.% Of a functional monomer.

Preferably, the functional monomer of the second preferred embodiment is a (meth) acrylic monomer. The functional monomer has the formula (1) or (2)

In both formulas (1) and (2), R ₁ is selected from H or CH ₃ ; In formula (1), Y is O and R < ₅ > is an aliphatic or aromatic radical having at least one atom which is not H or C or H; In formula (2), Y is N and R ₄ and / or R ₃ are H or an aliphatic or aromatic radical.

Preferably, the functional monomer (1) or (2) is selected from the group consisting of glycidyl (meth) acrylate, acrylic or methacrylic acid, amides derived from such acids such as dimethylacrylamide, Acrylate or methacrylate monomers comprising 2-aminoethyl acrylate or methacrylate (optionally quaternized), a phosphonate or phosphate group, alkylimidazolidinone (meth) acrylate (Meth) acrylate, and polyethylene glycol (meth) acrylate. Preferably, the polyethylene glycol group of the polyethylene glycol (meth) acrylate has a molecular weight in the range of 400 g / mol to 10 000 g / mol.

The multistage polymer according to the present invention has two or more stages different in its polymer composition.

The multistage polymer is preferably in the form of polymer particles which are considered spherical particles. These particles are also referred to as core shell particles. The first stage forms the core, and the second or all subsequent stages form respective shells. The aforementioned multistage polymer, also referred to as core / shell particles, is preferred.

With respect to the polymeric particles according to the invention, which are primary particles , their weight average particle size (diameter) is from 15 nm to 900 nm. Preferably the weight average particle size of the polymer is from 20 nm to 800 nm, more preferably from 25 nm to 600 nm, even more preferably from 30 nm to 550 nm, even more preferably from 35 nm to 500 nm, advantageously from 40 nm to 400 nm More advantageously from 75 nm to 350 nm and advantageously from 80 nm to 300 nm. The primary polymer particles can agglomerate to produce a polymer powder comprising a multistage polymer or (meth) acrylic polymer (P1) and a multistage polymer.

The polymer particles may be obtained by a process comprising a multistage process, for example two, three or more stages.

The polymer particles can be prepared by mixing one or more layers (A) comprising a polymer (A1) having a glass transition temperature of less than 0 DEG C and another layer (B) comprising a polymer (B1) having a glass transition temperature of greater than 30 DEG C Layer structure.

In a first preferred embodiment, the polymer (B1) having a glass transition temperature of at least 30 DEG C is an outer layer of polymer particles having a multilayer structure.

In a second preferred embodiment, the polymer (B1) having a glass transition temperature of at least 30 占 폚 is an intermediate layer of polymer particles having a multilayer structure, before the multistage polymer is contacted with the monomer (M1).

Preferably, stage (A) is the first stage and stage (B) comprising polymer (B1) is grafted onto stage (A) comprising polymer (A1) or another intermediate layer. The first stage means that the stage (A) comprising the polymer (A1) is prepared before the stage (B) comprising the polymer (B1).

In layer (A), polymer (A1) having a glass transition temperature of less than 0 占 폚 is never made during the last step of the multistage process. This means that the polymer (A1) is never present in the outer layer of a multi-layered particle. Polymer (A1) having a glass transition temperature of less than 0 占 폚 in layer (A) is in one of the core or the inner layer of polymer particles.

Preferably, the polymer (A1) having a glass transition temperature of less than 0 占 폚 in the layer (A) is used in the first step of the multistage process for forming the core for the polymer particles having a multilayer structure and / (B1) having a transition temperature. Preferably, the polymer (A1) has a glass transition temperature of less than -5 DEG C, more preferably less than -15 DEG C, advantageously less than -25 DEG C.

In a first preferred embodiment, the polymer (B1) having a glass transition temperature of greater than 60 DEG C is prepared in the last step of a multistage process to form an outer layer of polymer particles having a multilayer structure.

In a second preferred embodiment, the polymer (B1) having a glass transition temperature of 30 DEG C or higher is an intermediate layer of polymer particles having a multilayer structure and is produced in a step subsequent to the step of forming the polymer (A1) of the multistage process.

There may be additional intermediate layer (s) obtained by intermediate step (s).

The glass transition temperature Tg of each polymer can be estimated, for example, by a dynamic method as a thermo mechanical analysis.

To obtain samples of the respective polymers (A1) and (B1), they are prepared independently and in a multistage manner, so that the glass transition temperature Tg of each polymer of each step can be more easily estimated and measured .

With respect to polymer (A1), in a first embodiment, it is a (meth) acrylic polymer containing at least 50 wt% of monomer from alkyl acrylate.

More preferably, polymer (A1) comprises comonomer (s) that can be copolymerized with the alkyl acrylate as long as polymer (A1) has a glass transition temperature of less than 0 占 폚.

The comonomer (s) in polymer (A1) is preferably selected from (meth) acrylic monomers and / or vinyl monomers.

The (meth) acrylic comonomer in polymer (A1) comprises a monomer selected from C1 to C12 alkyl (meth) acrylates. Even more preferably, the (meth) acrylic comonomer in polymer (A1) comprises a monomer of C1 to C4 alkyl methacrylate and / or a C1 to C8 alkyl acrylate monomer.

Most preferably, the acrylic or methacrylic comonomer of the polymer (A1) is an acrylic or methacrylic comonomer selected from the group consisting of methyl acrylate, propyl acrylate, isopropyl acrylate, butyl acrylate , tert-butyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, and mixtures thereof.

Preferably, the polymer (A1) is crosslinked. This means that the crosslinking agent is added to the other monomer (s). The crosslinking agent comprises at least two groups that can be polymerized.

In one particular embodiment, polymer (A1) is a homopolymer of butyl acrylate.

In another particular embodiment, polymer (A1) is a copolymer of butyl acrylate and at least one crosslinker. The crosslinking agent represents less than 5 wt% of such a copolymer.

More preferably, the glass transition temperature Tg of the polymer (A1) of the first embodiment is in the range of -100 ° C to 0 ° C, more preferably -100 ° C to -5 ° C, advantageously -90 ° C to -15 ° C and More advantageously between -90 < 0 > C and -25 < 0 > C.

With respect to polymer (A1), in a second embodiment, polymer (A1) is a silicone rubber based polymer. For example, the silicone rubber is polydimethylsiloxane. More preferably, the glass transition temperature Tg of the polymer (A1) of the second embodiment is -150 ° C to 0 ° C, more preferably -145 ° C to -5 ° C, advantageously -140 ° C to -15 ° C and More advantageously -135 캜 to -25 캜.

With respect to polymer (A1), in a third embodiment, polymer (A1) having a glass transition temperature below 0 ° C comprises at least 50 wt% of polymeric units from isoprene or butadiene, wherein step (A) It is the innermost layer of polymer particles having a multilayer structure. In other words, the stage (A) comprising the polymer (A1) is the core of the polymer particles.

By way of example, the polymer A1 of the core of the second embodiment is a copolymer of an isoprene homopolymer or a butadiene homopolymer, an isoprene-butadiene copolymer, a copolymer of isoprene with up to 98 wt% vinyl monomer, and a copolymer of butadiene with up to 98 wt% May be mentioned. The vinyl monomer may be styrene, alkylstyrene, acrylonitrile, alkyl (meth) acrylate, or butadiene or isoprene. In one embodiment, the core is a butadiene homopolymer.

More preferably, the glass transition temperature Tg of the polymer (A1) of the third embodiment comprising at least 50 wt% of polymeric units from isoprene or butadiene is in the range of -100 DEG C to 0 DEG C, -5 ° C, advantageously -90 ° C to -15 ° C and even more advantageously -90 ° C to -25 ° C.

With respect to polymer (B1), mention may be made of homopolymers and copolymers comprising monomers having a double bond and / or vinyl monomers. Preferably, the polymer (B1) is a (meth) acrylic polymer.

Preferably, the polymer (B1) comprises at least 70 wt% of monomer selected from C1 to C12 alkyl (meth) acrylates. Even more preferably, the polymer (B1) comprises at least 80 wt% monomer C1 to C4 alkyl methacrylate and / or C1 to C8 alkyl acrylate monomer.

Polymer (B1) can be crosslinked.

Most preferably, the acrylic or methacrylic monomers of the polymer (B1) are selected from the group consisting of methyl acrylate, ethyl acrylate, butyl acrylate, methyl methacrylate, butyl acrylate, Ethyl methacrylate, butyl methacrylate, and mixtures thereof.

Advantageously, the polymer (B1) comprises at least 50 wt%, more advantageously at least 60 wt% and even more advantageously at least 70 wt% monomer units from methyl methacrylate.

Preferably, the glass transition temperature Tg of the polymer (B1) is from 30 캜 to 150 캜. The glass transition temperature of the polymer (B1) is more preferably from 50 캜 to 150 캜, still more preferably from 70 캜 to 150 캜, advantageously from 90 캜 to 150 캜 and more advantageously from 90 캜 to 130 캜.

In another embodiment, the multistage polymer described above has an additional end which is a (meth) acrylic polymer (Pl). The primary polymer particles according to this embodiment of the present invention comprise at least one stage (A) comprising a polymer (A1) having a glass transition temperature lower than 0 deg. C, a polymer (B1) having a glass transition temperature higher than 30 deg. At least one stage (B) and at least one stage (P) comprising a (meth) acrylic polymer (P1) having a glass transition temperature of 30 占 폚 to 150 占 폚.

Preferably, the (meth) acrylic polymer (P1) is not grafted onto any one of the polymers (A1) and (B1).

In connection with the process for preparing a multistage polymer according to the invention, this comprises the following steps:

a) to obtain at least one layer (A) comprising a polymer (A1) having a glass transition temperature less than 0 ℃, a monomer or a polymerization stage by emulsion polymerization of a monomer mixture (A _m),

b) a polymerization step by emulsion polymerization of a monomer or mixture of monomers (B _m ) to obtain a layer (B) comprising a polymer (B1) having a glass transition temperature of at least 30 DEG C,

The monomer or mixture of monomers (A _m ) and the monomer or mixture of monomers (B _m ) are selected from the monomers according to the composition relating to polymer (A1) and polymer (B1) given above.

Preferably step a) is carried out before step b). More preferably, step b) is carried out in the presence of the polymer (A1) obtained in step a) when there are only two steps.

Advantageously, the process for preparing a multistage polymer composition according to the present invention is a multistage process which in turn comprises the following steps:

a) polymerization step of the emulsion polymerization of a layer (A), the monomer or monomer mixture (A _m) for obtaining containing polymer (A1) having a glass transition temperature less than 0 ℃,

b) a polymerization step by emulsion polymerization of a monomer or mixture of monomers (B _m ) to obtain a layer (B) comprising a polymer (B1) having a glass transition temperature of at least 30 캜.

Each monomer or monomer mixture (A _m ) and (A _m ) to form each of the polymers (A1) and (B1) and each of the layers (A) and (B) comprising the polymers (A1) and B _m ) are the same as defined above.

The method of making a multistage polymer may include additional steps for additional steps between steps a) and b).

Production method of the multi-stage polymer can also include additional steps for the additional steps prior to steps a) and b). Seed (seed) has been used in the polymerization by emulsion polymerization of a monomer or monomer mixture (A _m), it is possible to obtain a layer (A) comprising a polymer (A1) having a glass transition temperature less than 0 ℃. The seed is preferably a thermoplastic polymer having a glass transition temperature of at least 20 캜.

The multistage polymer is obtained as an aqueous dispersion of polymer particles. The solids content of the dispersion is from 10 wt% to 65 wt%.

In relation to the production method of the (meth) acrylic polymer (P1) according to the invention, which comprises a polymerization step in each of the (meth) acrylic monomer _(m P1). Each of the (meth) acrylic monomer _(m P1) are the same as defined previously with respect to two preferred embodiments of the (meth) acrylic polymer (P1) and (meth) acrylic polymer (P1).

(Meth) acrylic alone or copolymer (P1) can be prepared by a batch or semi-continuous process:

In the case of a batch process, the mixture of monomers is introduced in one shot just before or after the introduction of one or a portion of the initiator system,

In the case of a semi-continuous process, the monomer mixture may be added several times or continuously in the course of a defined addition period, which may range from 30 to 500 min, with the addition of initiator (initiator is also added multiple shots or continuously) .

The (meth) acrylic polymer (P1) and the process for preparing a polymer composition comprising a multistage polymer have two preferred embodiments.

In a first preferred embodiment of the process, the (meth) acrylic polymer (P1) is polymerized in the presence of a multistage polymer. The (meth) acrylic polymer (P1) is prepared as an additional end of the multistage polymer.

In a second preferred embodiment of the process, the (meth) acrylic polymer (P1) is polymerized separately and blended or blended with the multi-stage polymer.

(Meth) weight average molecular weight of the acrylic polymer (P1) and the first with respect to the method according to the preferred embodiment, which comprises the steps of (meth) for the preparation of a polymer composition comprising a multi-stage polymer an acrylic polymer (P1) Characterized in that the Mw is less than 100 000 g / mol:

a) to obtain a single layer on a stage (A) comprising a polymer (A1) having a glass transition temperature less than 0 ℃, the polymerization stage by emulsion polymerization of a monomer or monomer mixture (A _m),

b) a polymerization step by emulsion polymerization of a monomer or mixture of monomers (B _m ) to obtain a layer in step (B) comprising a polymer (B1) having a glass transition temperature of at least 30 ° C,

c) (meth) acrylic polymer (P1) such to give the layer the additional stage, a monomer or monomer mixture _(m P1) polymerization in emulsion in the polymerization step by including a having a glass transition temperature of at least 30 ℃.

Preferably step a) is carried out before step b).

More preferably, step b) is carried out in the presence of the polymer (A1) obtained in step a).

Advantageously, the process for preparing a polymer composition comprising a (meth) acrylic polymer (P1) and a multistage polymer is a multistage process which comprises, in sequence, the following steps, wherein the mass average molecular weight Mw of the (meth) acrylic polymer 000 g / mol.

a) a glass transition temperature by emulsion polymerization in stage (A), the monomer or monomer mixture (A _m) to obtain a layer containing the polymer (A1) is less than 0 ℃ polymerization step,

b) a polymerization step by emulsion polymerization of a monomer or mixture of monomers (B _m ) to obtain a layer in step (B) comprising a polymer (B1) having a glass transition temperature of at least 30 ° C,

c) Polymerization step by emulsion polymerization of a monomer or mixture of monomers (P1 _m ) to obtain a layer in this additional stage comprising a (meth) acrylic polymer (P1) having a glass transition temperature of at least 30 캜.

(A _m ), (B _m ), and (P1) for forming each of the layers (A), (B) and the additional layers each comprising the polymers (A1), (B1) and _m ) are as defined previously. The characteristics of each of the polymers (A1), (B1) and (P1) are the same as previously defined.

Preferably, the process for preparing a polymer composition comprising a (meth) acrylic polymer (P1) and a multistage polymer comprises a further step d) of recovering such a polymer composition.

Recovery refers to partial or separation between the aqueous phase and the solid phase (the latter including the polymer composition).

More preferably according to the invention, the recovery of the polymer composition is effected by coagulation or spray-drying.

Spray drying is preferably carried out when the polymer (A1) having a glass transition temperature of less than 0 DEG C comprises at least 50 wt% polymeric units from alkyl acrylate and the stage (A) is the innermost layer of the polymer particles having a multilayer structure , And a method for recovering and / or drying a polymer powder composition.

When the polymer (A1) having a glass transition temperature of less than 10 DEG C contains at least 50 wt% polymeric units from isoprene or butadiene and the stage (A) is the innermost layer of the polymer particles having a multilayer structure, And / or a drying method preferable for the method for producing a polymer powder composition according to the present invention.

The process for preparing the polymer composition according to the invention optionally comprises a further step e) of drying the polymer composition.

Preferably, the drying step e) is carried out when step d) of recovering the polymer composition is carried out by agglomeration.

Preferably, the polymer composition after drying step e) comprises less than 3 wt%, more preferably less than 1.5 wt%, advantageously less than 1% humidity or water.

The humidity of the polymer composition can be measured with a thermo balance.

Drying of the polymer can be done in an oven or vacuum oven with heating of the composition at 50 캜 for 48 hours.

With respect to the process according to the second preferred embodiment for the production of a polymer composition comprising a (meth) acrylic polymer (P1) and a multistage polymer, it comprises the following steps:

a) mixing of the (meth) acrylic polymer (P1) and the multistage polymer,

b) recovery of the mixture of the previous steps obtained in the form of a polymer powder,

Here, the (meth) acrylic polymer (P1) and the multistage polymer in step a) are in the form of a dispersion in an aqueous phase.

The amount of the aqueous dispersion of the (meth) acrylic polymer (P1) and the aqueous dispersion of the multistage polymer is such that the weight ratio of the multistage polymer based on solids only in the resulting mixture is at least 5 wt%, preferably at least 10 wt% Is at least 20 wt% and advantageously at least 50 wt%.

The amount of the aqueous dispersion of the (meth) acrylic polymer (P1) and the aqueous dispersion of the multistage polymer is such that the weight ratio of the multistage polymer based on solids portion in the resulting mixture is at most 99 wt%, preferably at most 95 wt% Is selected at a maximum of 90 wt%.

The amount of the aqueous dispersion of the (meth) acrylic polymer (P1) and the aqueous dispersion of the multistage polymer is preferably from 5 wt% to 99 wt%, more preferably from 10 wt% to 95 wt%, based on the solids portion, And more preferably 20 wt% to 90 wt%.

The recovery step b) of the process for producing the polymer composition comprising the (meth) acrylic polymer (P1) and the multistage polymer is preferably carried out by coagulation or spray drying.

The process for preparing a polymer composition comprising (meth) acrylic polymer (P1) and a multistage polymer optionally comprises a further step c) for drying the polymer composition.

Drying means that the polymer composition according to the present invention comprises less than 3 wt% humidity, preferably less than 1.5 wt% humidity, and more preferably less than 1.2 wt% humidity.

Humidity can be measured by heating the polymer composition and measuring the weight loss by a thermal balance.

The process for producing a polymer composition comprising a (meth) acrylic polymer (P1) and a multistage polymer preferably obtains a polymer powder. The polymer powder of the present invention is in the form of particles. The polymer powder particles comprise agglomerated primary polymer particles and a (meth) acrylic polymer (P1) prepared by a multistage process.

With respect to the polymer powder comprising the (meth) acrylic polymer (P1) and the multistage polymer according to both embodiments of the production process , it has a volume median particle size D50 of 1 to 500 m. Preferably, the volume median particle size of the polymer powder is from 10 占 퐉 to 400 占 퐉, more preferably from 15 占 퐉 to 350 占 퐉, and advantageously from 20 占 퐉 to 300 占 퐉.

The D10 of the particle size distribution in volume is at least 7 mu m and preferably 10 mu m.

The D90 of the particle size distribution in volume is up to 950 [mu] m, and preferably 500 [mu] m, more preferably up to 400 [mu] m.

The weight ratio r of the (meth) acrylic polymer (P1) relative to the multistage polymer is at least 5 wt%, more preferably at least 7 wt%, and even more preferably at least 10 wt%.

According to the present invention, the ratio r of the (meth) acrylic polymer (P1) relative to the multistage polymer is at most 95 wt%.

Preferably, the weight ratio of the (meth) acrylic polymer (P1) relative to the multistage polymer is from 5 wt% to 95 wt% and preferably from 10 wt% to 90 wt%.

With respect to the (meth) acrylic monomer (M1), it is a liquid monomer at a temperature range of at least 0 캜 to 60 캜. (Meth) acrylic monomer (M1) contains one carbon C = C double bond.

The (meth) acrylic monomer (M1) according to the present invention is a monomer which is a solvent for the (meth) acrylic polymer (P1). In other words, the (meth) acrylic polymer (P1) is soluble in the (meth) acrylic monomer (M1).

The solubility is such that at a specific time, the (meth) acrylic polymer P1 in contact with the thermodynamically compatible (meth) acrylic monomer (M1) is dissolved and the (meth) acrylic polymer P1 of the (meth) acrylic monomer ) ≪ / RTI > is obtained.

The solubility of the (meth) acrylic polymer (P1) in the (meth) acrylic monomer (M1) can be tested simply by mixing the two compounds under shaking at 25 ° C. Solvents containing monomers as (meth) acrylic monomers (M1) for a number of polymers are known to those skilled in the art. On the other hand, solubility parameter values are given for a large number of polymers and solvents, the latter containing a number of monomers are described, for example, in Polymer Handbook (4 ^th edition) Ed. J. Brandrup, EH Immergut and EA Grulke; Pub .: John Wiley and Sons Inc. 1999, Chapter "Solubility Parameter Value" by Eric A. Gulke VII / 675 to VII / 714.

The (meth) acrylic monomer (M1) is selected from (meth) acrylic monomers and mixtures thereof. When the (meth) acrylic monomer (M1) is a mixture of several monomers, the (meth) acrylic polymer (P1) is soluble in the mixture comprising the (meth) acrylic monomer (s) (M1).

The (meth) acrylic monomer (M1) is more preferably selected from acrylic acid, methacrylic acid, alkyl acryl monomers, alkyl methacryl monomers and mixtures thereof.

More preferably, the (meth) acrylic monomer (M1) is selected from the group consisting of acrylic acid, methacrylic acid, alkyl acryl monomers, alkyl methacrylic monomers and mixtures thereof, linear, branched or cyclic alkyl groups of 1 to 22 carbon atoms; Preferably a linear, branched, or cyclic alkyl group having 1 to 12 carbon atoms.

Advantageously, the (meth) acrylic monomer (M1) is selected from the group consisting of methyl methacrylate, ethyl methacrylate, methyl acrylate, ethyl acrylate, methacrylic acid, acrylic acid, n-butyl acrylate, isobutyl acrylate, n -Butyl methacrylate, iso-butyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, isobornyl acrylate, isobornyl methacrylate, and mixtures thereof.

More advantageously, the (meth) acrylic monomer (M1) is selected from methyl methacrylate, isobornyl acrylate or acrylic acid and mixtures thereof.

In a first most advantageous embodiment, at least 50 wt%, preferably at least 60 wt%, of the (meth) acrylic monomer (M1) is methyl methacrylate.

In a second most advantageous embodiment, at least 50 wt%, preferably at least 60 wt%, more preferably at least 70 wt% and advantageously at least 80 wt% and even more advantageously 90 wt% of the (meth) acrylic monomer (M1) Is a mixture of methyl methacrylate and isobornyl acrylate and / or acrylic acid.

The liquid composition of the present invention is less viscous than the composition that does not include the (meth) acrylic polymer (P1).

The liquid composition of the present invention can be used to prepare a more dispersed multistage polymer instead of a composition that does not include the (meth) acrylic polymer (P1).

With regard to the process for preparing a liquid composition, it comprises the following steps:

a) preparing a composition comprising a (meth) acrylic polymer (P1) and a multistage polymer,

b) mixing the composition of the previous step with (meth) acrylic monomer (M1)

Here, the weight ratio of the multistage polymer to the (meth) acrylic monomer (M1) in the liquid composition is 1/99 to 25/75.

Preferably, the mass average molecular weight Mw of the (meth) acrylic polymer (P1) is less than 100 000 g / mol. The (meth) acrylic polymer (P1) is the same as previously defined.

The composition comprising the (meth) acrylic polymer (P1) and the multistage polymer may be in the form of a polymer powder as obtained by two preferred manufacturing embodiments.

The process results in a liquid composition that is less viscous than a composition that does not include the (meth) acrylic polymer (P1).

The process yields a liquid composition having a better dispersion of the multistage polymer than the composition that does not comprise the (meth) acrylic polymer (P1).

The agglomerated polymer powder is better dispersed in the solvent when (meth) acrylic polymer (P1) is present.

The process of the present invention for the preparation of liquid compositions can be used to prepare multistage polymers that are better dispersed than compositions that do not contain (meth) acrylic polymer (P1).

A further aspect of the present invention is that the liquid composition comprising (a) can be used to prepare a dispersion of a multistage polymer in a more preferred monomer (M1) than a composition that does not comprise a (meth) acrylic polymer (P1)

a) a (meth) acrylic polymer (P1),

b) a multistage polymer, and

c) (meth) acrylic monomer (M1),

Here, the weight ratio of the multistage polymer to the monomer (M1) in the liquid composition is 1/99 to 25/75.

Yet another further aspect of the present invention is that the liquid composition comprising (a) can be used in the preparation of impact modified polymers by polymerization of (meth) acrylic monomer (M1)

a) a (meth) acrylic polymer (P1),

b) a multistage polymer, and

c) (meth) acrylic monomer (M1),

Wherein the multistage polymer to monomer weight ratio in the liquid composition is from 1/99 to 25/75.

The liquid composition according to the present invention may also be mixed with other monomers and polymers that are not part of the liquid composition prior to polymerization. The liquid composition according to the present invention can be used as a liquid master batch.

The multistage polymer is better dispersed in the polymer matrix after polymerization than using a composition that does not include (meth) acrylic polymer (P1).

Another further aspect of the present invention is that the liquid composition comprising (a) is preferably used as an impregnating liquid (meth) acrylic syrup for a fibrous substrate;

a) a (meth) acrylic polymer (P1),

b) a multistage polymer, and

c) (Meth) acrylic monomer (M1)

Wherein the multistage polymer to monomer weight ratio in the liquid composition is from 1/99 to 25/75.

Another further aspect of the present invention is a process for preparing a liquid composition for an impregnating liquid for an impregnating liquid, preferably a fibrous substrate, in the form of a (meth) acrylic syrup, comprising the following steps:

a) preparing a composition comprising a (meth) acrylic polymer (P1) and a multistage polymer,

b) mixing the composition of the previous step and the (meth) acrylic monomer (M1)

Here, the weight ratio of the multistage polymer to the monomer (M1) in the liquid composition is 1/99 to 25/75.

Yet another further aspect of the present invention relates to a method of impregnation for impregnation of a fibrous substrate wherein the fibrous substrate comprises long fibers and the method comprises the impregnation of the fibrous substrate with a liquid composition comprising Step:

a) a (meth) acrylic polymer (P1),

b) a multistage polymer, and

c) (meth) acrylic monomer (M1),

Wherein the multistage polymer to monomer weight ratio in the liquid composition is from 1/99 to 25/75.

Another further aspect of the present invention relates to the use of a liquid composition in an impregnation method for impregnation of a fibrous substrate, comprising:

a) a (meth) acrylic polymer (P1),

b) a multistage polymer, and

c) (Meth) acrylic monomer (M1)

Wherein the multistage polymer to monomer weight ratio in the liquid composition is from 1/99 to 25/75.

Preferably, the fibrous substrate comprises long fibers.

The liquid composition according to the invention can be used as a liquid masterbatch for use in impregnation methods for impregnation of fibrous substrates or as impregnated liquid (meth) acrylic syrups.

With regard to the fibrous substrate , a fabric, felt or nonwoven which may be in the form of a strip, a lap, a braid, a lock or a piece can be mentioned. The fibrous material can have different shapes and one, two or three dimensional dimensions. The fibrous substrate comprises an assembly of one or more fibers. If the fibers are continuous, their assemblies form a fabric.

The one-dimensional form is a linear long fiber. The fibers can be discontinuous or continuous. The fibers can be arranged as parallel filaments parallel to one another or randomly. The fiber is defined by its aspect ratio, which is the ratio between the length and diameter of the fiber. The fibers used in the present invention are long fibers or continuous fibers. The fibers have an aspect ratio of at least 1000, preferably at least 1500, more preferably at least 2000, advantageously at least 3000 and most advantageously at least 5000.

The two-dimensional form is a fibrous mat or a nonwoven reinforcement, or a bundle of woven roving or fibers, which may also be twisted.

The three-dimensional form is, for example, a two-dimensional, three-dimensional assembly of a stacked or folded fibrous mat or a bundle of nonwoven reinforcing materials or fibers, or a mixture thereof.

The origin of the fibrous material may be natural or synthetic origin. As a natural substance, vegetable fiber, wood fiber, animal fiber or mineral fiber can be mentioned.

Natural fibers are, for example, sisal, jute, hemp, flax, cotton, coconut fiber and banana fibers. Animal fibers are, for example, wool or hair.

As synthetic materials, polymeric fibers selected from fibers of thermosetting polymers, thermoplastic polymers or mixtures thereof may be mentioned.

The polymeric fibers may be made of polyamide (aliphatic or aromatic), polyester, polyvinyl alcohol, polyolefin, polyurethane, polyvinyl chloride, polyethylene, unsaturated polyester, epoxy resin and vinyl ester.

Mineral fibers may also be selected, in particular, from glass fibers of the type E, R or S2, carbon fibers, boron fibers or silica fibers.

The fibrous substrate of the present invention is selected from vegetable fibers, wood fibers, animal fibers, mineral fibers, synthetic polymeric fibers, glass fibers, carbon fibers or mixtures thereof.

Preferably, the fibrous substrate is selected from mineral fibers.

[Assessment Methods]

Viscosity measurement

The viscosity is measured by an MCR 301 flow meter manufactured by Anton Paar. Couette geometry is used. The temperature is 25 ° C and the shear rate is 0.1 s ^-1 to 100 s ^-1 .

Glass transition temperature

The glass transition (Tg) of the polymer is measured by equipment capable of thermo-mechanical analysis. The RDAII "RHEOMETRICS DYNAMIC ANALYZER" proposed by the Rheometrics Company is used. The thermomechanical analysis accurately measures the change in the viscoelasticity of the sample as a function of applied temperature, strain or deformation. The apparatus continuously records the sample deformation while maintaining a fixed strain during the program of controlled temperature change.

The results are obtained as a function of temperature, elastic modulus (G '), loss modulus and tan delta as a function of the figure. Tg is the higher temperature value read from the tan delta curve when the derive of tan delta is zero.

Molecular Weight

The mass average molecular weight (Mw) of the polymer is measured by size exclusion chromatography (SEC).

Particle size analysis

The particle size of primary particles after multistage polymerization is measured by a Zetasizer.

The particle size of the polymer powder after recovery is measured by a Malvern Mastersizer 3000 manufactured by MALVERN.

For the estimation of the weight average particle size, particle size distribution and fraction of particles, a Malvern Mastersizer 3000 instrument equipped with a 300 mm lens is used, which measures the range of 0,5-880 mu m.

[Example]

Synthesis of a multistage polymer (core-shell particle) is made according to the embodiment of sample 1 of WO2012 / 038441 to obtain a multistage polymer. A multistage polymer CS1 is obtained. (A) having a glass transition temperature of less than 0 DEG C (consisting essentially of butyl acrylate) and a polymer (B1) having a glass transition temperature of at least 30 DEG C (consisting essentially of methyl methacrylate (B) that includes a rate (e.g. The multistage polymer CS1 is maintained as an aqueous dispersion for further use.

The synthesis of the (meth) acrylic polymer type (P1) is according to two embodiments: First, the (meth) acrylic polymer (P1) is polymerized in the presence of the multistage polymer CS1. (Meth) acrylic polymer (P1) is prepared as an additional end of the multistage polymer CS. And in the second embodiment, the (meth) acrylic polymer (P1) is polymerized separately and blended or blended with the multistage polymer after termination of the polymerization of the (meth) acrylic polymer (P1).

Comparative Example 1: Multistage polymer CS1 is mixed with methyl methacrylate (MMA) at 20 占 폚 under shaking such that 15 wt% CS1 is present in the liquid composition as compared to MMA.

Example 1: (Meth) acrylic polymer (P1) is prepared as an additional end on multistage polymer CS1. The mass average molecular weight of the (meth) acrylic polymer P1 is M _w = 28 000 g / mol.

The final polymer composition was then recovered and the polymer composition dried by spray drying. The resultant polymer composition was prepared from methyl methacrylate (MMA) at 20 占 폚 under shaking so that 15 wt% of CS1 relative to MMA was present in a liquid composition comprising MMA, (meth) acrylic polymer (P1) and multi- ≪ / RTI >

Example 2: The (meth) acrylic polymer (P1) is polymerized separately and mixed or blended with the multistage polymer CS1. Synthesis of (meth) acrylic polymer (P1): semi-continuous method: 1700 g of deionized water, 0.01 g of FeSO ₄ and 0.032 g of ethylenediaminetetraacetic acid, sodium salt (dissolved in 10 g of deionized water) Sodium formaldehyde sulfoxylate (dissolved in 110 grams of deionized water) and 21.33 grams of emulsifying agent potassium salt of the beef tallow fatty acid (dissolved in 139.44 grams of water) were charged to the reactor with stirring, It was stirred until complete dissolution. Three vacuum-nitrogen purges were performed in succession, and the reactor was placed under slight vacuum. The reactor was then heated. At the same time, a mixture comprising 960.03 g of methyl methacrylate, 106.67 g of dimethyl acrylamide and 10.67 g of n-octyl mercaptan was nitrogen-degassed for 30 minutes. The reactor is heated at 63 DEG C and held at this temperature. Next, the monomer mixture was introduced into the reactor within 180 min using a pump. In parallel, a solution of 5.33 g of tert-butyl hydroperoxide (dissolved in 100 g of deionized water) is introduced (same addition time). The lines were rinsed with 50 g and 20 g of water. The reaction mixture was then heated at a temperature of 80 DEG C and the polymerization was then allowed to complete for 60 minutes after the end of monomer addition. The reactor was cooled below 30 ° C. The obtained solid content is 34.2%. The mass average molecular weight of the (meth) acrylic polymer P1 is M _w = 28 000 g / mol.

 The aqueous dispersion of the multistage polymer CS1 and the (meth) acrylic polymer (P1) is mixed in an amount of 15/85 by weight based on the solid polymer, between the (meth) acrylic polymer (P1) and the multistage polymer CS1. The mixture was recovered as powder by spray drying.

The resulting mixture is mixed with methyl methacrylate at 20 占 폚 under shaking such that 15 wt% of CS1 relative to MMA is in a liquid composition comprising MMA, (meth) acrylic polymer (P1) and multistage polymer CS1.

Example 3: Example 2 is repeated except that the weight ratio between the (meth) acrylic polymer (P1) and the multistage polymer CS1, based on the solid polymer, is 25/75.

The viscosity of each liquid composition is measured.

Table 1 - Viscosity Results

As shown in Table 1, the total solids content of the polymer increases while the proportion of core-shell polymer remains constant at 15 wt% compared to the monomers, but the dynamic viscosity of the composition decreases.

The core shell particles are more effectively dispersed when the methacrylic polymer is present and have a lower effective volume in the liquid composition.

The glass fiber mat is impregnated by the infusion method using the liquid composition according to the embodiment more easily and quickly than with the composition according to the comparative example.

Claims (30)

A liquid composition comprising:
a) a (meth) acrylic polymer (P1),
b) a multistage polymer, and
c) (Meth) acrylic monomer (M1)
Wherein the multistage polymer to monomer weight ratio in the liquid composition is from 1/99 to 25/75. The liquid composition according to claim 1, wherein the mass average molecular weight Mw of the (meth) acrylic polymer (P1) is less than 100 000 g / mol. The liquid composition according to claim 1, wherein the mass average molecular weight Mw of the (meth) acrylic polymer (P1) is less than 50,000 g / mol. The liquid composition according to claim 1, wherein the mass average molecular weight Mw of the (meth) acrylic polymer (P1) is greater than 5 000 g / mol. 2. A liquid (1) as claimed in claim 1, characterized in that the mass average molecular weight Mw of the (meth) acrylic polymer (P1) is from 5 000 g / mol to 70 000 g / mol, more advantageously from 6 000 g / mol to 50 000 g / Composition. The ratio of multistage polymer to monomer in the liquid composition is preferably from 2/98 to 24/76, more preferably from 3/97 to 23/77, even more preferably from 4/96 to 22/78 and advantageously from 5/95 to 20 / 80. The liquid composition according to any one of claims 1 to 3, characterized in that the (meth) acrylic polymer (P1) is soluble in the (meth) acrylic monomer (M1). 8. The composition according to any one of claims 1 to 7, wherein the monomer (M1) is selected from the group consisting of acrylic acid, methacrylic acid, alkyl acryl monomers, alkyl methacrylic monomers and mixtures thereof, linear, branched or cyclic Alkyl groups; Preferably linear, branched or cyclic alkyl groups of 1 to 12 carbon atoms. 8. The composition according to any one of claims 1 to 7, wherein the monomer (M1) is at least one monomer selected from the group consisting of methyl methacrylate, ethyl methacrylate, methyl acrylate, ethyl acrylate, methacrylic acid, acrylic acid, Is selected from the group consisting of butyl acrylate, n-butyl methacrylate, iso-butyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, isobornyl acrylate, isobornyl methacrylate and mixtures thereof ≪ / RTI > 10. Liquid composition according to any one of claims 1 to 9, characterized in that the multistage polymer comprises:
(a) comprising a) a polymer (A1) having a glass transition temperature lower than 0 占 폚,
b) one end (B) comprising a polymer (B1) having a glass transition temperature of at least 30 占 폚. A liquid according to claim 10, characterized in that the stage (A) is the first stage and the stage (B) comprising the polymer (B1) is grafted onto the stage (A) Composition. The liquid composition according to claim 10 or 11, characterized in that the polymers (A1) and (B1) are acrylic or methacrylic polymers. 12. The liquid composition according to claim 10 or 11, characterized in that the polymer (A1) comprises at least 50 wt% of polymeric units from isoprene or butadiene. 14. A process according to any one of claims 1 to 13, characterized in that the (meth) acrylic polymer (P1) comprises at least 50% by weight of a monomer selected from C1 to C12 alkyl (meth) Composition. 14. The composition according to any one of claims 1 to 13, wherein the (meth) acrylic polymer (P1) comprises 50 wt% to 100 wt% methyl methacrylate, preferably 80 wt% to 100 wt% methyl methacrylate, Characterized in that it comprises from 80 wt% to 99.8 wt% methyl methacrylate and from 0.2 wt% to 20 wt% C1 to C8 alkyl acrylate monomers. 14. The liquid composition according to any one of claims 1 to 13, characterized in that the (meth) acrylic polymer (P1) comprises from 0 wt% to 50 wt% of a functional monomer. 14. The liquid composition according to any one of claims 1 to 13, characterized in that the (meth) acrylic polymer (P1) comprises from 1 wt% to 30 wt% of a functional monomer. 14. The composition of claim 12 or 13, wherein the functional comonomer is selected from the group consisting of glycidyl (meth) acrylate, acrylic or methacrylic acid, amides derived from such acids such as dimethylacrylamide, Acrylate or methacrylate monomers comprising ethyl acrylate or methacrylate, 2-aminoethyl acrylate or methacrylate (optionally quaternized), phosphonate or phosphate groups, alkylimidazolidinone (meth) acrylates (Meth) acrylate, and preferably the polyethylene glycol group of the polyethylene glycol (meth) acrylate has a molecular weight in the range of 400 g / mol to 10 000 g / mol. A process for preparing a liquid composition according to any one of claims 1 to 18, comprising the following steps:
a) preparing a composition comprising a (meth) acrylic polymer (P1) and a multistage polymer,
b) mixing the composition of the previous step and (meth) acrylic monomer (M1)
Wherein the ratio of multistage polymer to monomer in the liquid composition is from 1/99 to 25/75. 20. The process according to claim 19, wherein the mass average molecular weight Mw of the (meth) acrylic polymer (P1) is less than 100 000 g / mol. 20. The process according to claim 19, wherein the mass average molecular weight Mw of the (meth) acrylic polymer (P1) is from 5 000 g / mol to 70 000 g / mol. 20. The process according to claim 19, wherein the mass average molecular weight Mw of the (meth) acrylic polymer (P1) is from 6 000 g / mol to 50 000 g / mol. A method of impregnating a fibrous substrate, the method comprising impregnating the fibrous substrate with a liquid composition comprising long fibers, the method comprising:
a) a (meth) acrylic polymer (P1),
b) a multistage polymer, and
c) (meth) acrylic monomer (M1),
Wherein the multistage polymer to monomer weight ratio in the liquid composition is from 1/99 to 25/75. The impregnation method according to claim 23, wherein the mass average molecular weight Mw of the (meth) acrylic polymer (P1) is less than 100 000 g / mol. The impregnation method according to claim 23, wherein the mass average molecular weight Mw of the (meth) acrylic polymer (P1) is from 5 000 g / mol to 70 000 g / mol. The impregnation method according to claim 23, wherein the mass average molecular weight Mw of the (meth) acrylic polymer (P1) is from 6 000 g / mol to 50 000 g / mol. A liquid composition according to any one of claims 1 to 18, which is obtained by the process according to any one of claims 19 to 26 for the preparation of a better dispersion of the multistage polymer in monomer (M1) Usage. Use of a liquid composition according to any one of claims 1 to 18, obtained by the process according to any one of claims 19 to 26 for the production of impact-modified polymers. A liquid composition according to any one of claims 1 to 18, which is obtained by the process according to any one of claims 19 to 26 as impregnating liquid (meth) acrylic syrup, preferably for a fibrous substrate Use of. Use of a liquid composition according to any one of claims 1 to 18, obtained by the process according to any one of claims 19 to 26, in an impregnation method for impregnation of fibrous substrates.